Fuels & Thermochemistry | Topic Notes Fuel and Heats of ... · fuels than hydrocarbons as there are...
Transcript of Fuels & Thermochemistry | Topic Notes Fuel and Heats of ... · fuels than hydrocarbons as there are...
Fuels & Thermochemistry | Topic Notes
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Fuels & Thermochemistry | Topic Notes
Fuel and Heats of Reactions.
• Crude Oil is a fossil fuel and formed from the bodies of tiny sea creatures that died
millions of years ago, as the layers of mud and slit grew thicker over the years, the
decay caused by bacteria slowly turned these bodies into crude oil and natural
gas.
• It is separated into a number of useful mixtures through a process called Fractional
Distillation.
• This involves heating the crude
oil and separating the various
mixtures on the basis of their
boiling points, each one of
these useful mixtures is called a
fraction.
• The crude oil is heated in the furnace
and enters the fractionating column as
a partially vapourised mixture.
• The fractionating column is a
tall cylindrical tower containing a
series of trays to help collect
the condensed liquids.
• Maintained at high temperature
at the bottom and the temperature decreases up along the
column.
• The larger hydrocarbons with higher boiling points turn to liquids near the bottom
of the column.
• The smaller hydrocarbons remain as gases and rise up along the column.
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• Different fractions condense at different levels in the fractionating column.
• Real - Refinery gas, bottled for sale as domestic gas, fuel C1 - C4
• People - Petrol or light gasoline, motor fuel C5 - C10
• Never - Naphtha - petrochemical industry, medicines, plastics, solvents and
synthetic fibres C7 - C10
• Kick - Kerosene - aviation fuel and in stoves C10 - C14
• Dirty - diesel oil, fuel in trucks, buses, trains and some cars C14 - C19
• Little - Lubricating oil - reduces wear of engines C10 - C35
• F****** - Fuel Oil - ships, power stations and heating plants C30 - C40
• B****** - bitumen - road surfacing/tar, waterproofing and roofing. C35 <
Lubricating Oil, Bitumen and Fuel Oil are the residue fractions, these are the
fractions that are left over when the more volatile fractions boil off.
Mercaptens are sulfur compounds that are added to odourless gases such as
refinery gases so that gas leaks can be detected.
Octane Number is a measure of a fuels tendency to resist knocking or auto
ignition measured on a scale of 100 being assigned to 2,2,4 trimethylpentane
and 0 being assigned to heptane.
• The early explosion of the petrol air mixture in the car’s cylinder is auto ignition or
‘knocking’, the engine can lose power and the cylinders can be damaged as a
result, the pistons vibrate and a metallic noise is heard.
• The shorter the alkane chain the higher the ON rating
• The more branched the alkane chain, the higher the ON rating
• Cyclic compounds have a higher ON than straight chain compounds
Tetraethyl lead was used in 1920’s as an anti-knock additive, lead pollution from car
exhausts had the potential to cause health damage. This lead to ‘unleaded petrol’
Fuels & Thermochemistry | Topic Notes
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Lead compounds are toxic and poison metal catalysts in the catalytic converter
which means they can no longer reduce levels of pollutants in exhaust fumes.
Isomerisation
Involves changing straight chain alkanes into their isomers.
• The alkanes are heated in the presence of a suitable catalyst and this causes
chains to break. When they do they are allowed to rejoin together and as a result
they are more likely to become branched chain alkanes as opposed to straight
chain alkanes.
• The straight chain alkanes are then again recycled over a suitable catalyst that
converts them to branched chain alkanes
• Pentane and hexane
Catalytic Cracking
Involves the breaking down of long chain hydrocarbon molecules to short
chain hydrocarbon molecules for which there is a greater demand.
• Short chain hydrocarbons are used in petrol - huge demand, they tend to be highly
branched which also increases the octane number.
• Involves heating heavier fractions in the presence of a catalyst
• A common reaction is when an alkane is converted into an alkene and a branched
alkane. If you split a saturated alkane atleast one product is unsaturated.
• Alkenes are important feedstock for petrochemicals industry - polythene,
polypropene etc...
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Reforming or Dehydrocyclisation
Involves the use of catalysts to form ringed compounds.
• Straight chain alkanes are converted to cycloalkanes and then cycloalkanes are
converted to aromatic compounds. Petrol contains 3/4% benzene - high ON.
Adding Oxygenates
any fuel that contains oxygen in its molecules, eg. methanol, ethanol, MTBE
(methyl tertiary butyl ether).
Increases octane number AND gives rise to very little pollution. They are cleaner
fuels than hydrocarbons as there are less carbon monoxide in exhaust of cars
(Brazil, ethanol)
Hydrogen gas is another fuel. There are 2 methods of manufacturing it:
(I) Steam reforming of natural gas - CH4 + H20 = 3H2 +CO, reacting methane
with steam in presence of suitable catalyst.
(II) Electrolysis of water - H20 -------> H2 +0.502, more expensive because of
high electricity costs
Burning hydrogen is very environmentally friendly - only by product is water, used to
manufacture ammonia, hydrogenating vegetable oils in making margarine.
hydrogen forms an explosive mixture with air so there are problems with storage
and transport.
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Thermochemistry
Exothermic - any chemical reaction that produces heat is exothermic and is represented by -
delta H. MINUS DELTA H. e.g. burning of food inside the body, the reaction of sodium dichromate
and ethanol.
Endothermic - a reaction that takes in heat - + Delta H. e.g. sherbert with water
Heat of reaction is the heat change that takes place when the number of moles of reactants
indicated in the balanced equation for the reaction react completely.
Thermochemical equations must be balanced, the value of delta H must be written and the
states of reactants and products must be given, e.g. gas, liquid etc...
Heat of combustion is the heat change that takes place when 1 mole of a substance is
completely burned in excess oxygen.
(general term)
important notes:
• C + 1/2O2 --------> CO delta H = -111kJmol^-1 This is not the heat of combustion because when
carbon is COMPLETELY burned in excess oxygen it forms carbon DIOXIDE not carbon
monoxide.
• Heat of combustion is measured using a bomb calorimeter.
• Small steel container with a screw on cap, the sample is placed in the crucible, the bomb is
placed in the container of water (calorimeter), oxygen is pumped into the bomb and the sample
is ignited by the electric wires.
• Bomb calorimeters also compare the efficiency of various fuels and gives the kilogram calorific
value of substances with a variable composition (coal, petrol, peat).
The kilogram calorific value of a fuel is the heat energy produced when 1kg of the fuel is
completely burned in oxygen.
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Bond energy is the energy required to break one mole of covalent bonds and to separate
the neutral atoms completely from each other.
Heat of neutralisation is the heat change that takes place when 1 mole of H+ ions from an
acid react with 1 mole of OH- ions from a base.
Heat liberated = M X C X (T1-T2)
C = specific heat capacity.
REMEBER MASS IS IN KILOGRAMS
• When 200 cm^3 NaOH solution was added to 200 cm^3 of a 0.4M sulfuric acid solution, a
neutral solution was produced and temperature increased by 5.5 degrees.
• C of neutral solution = 4.2 kJ kg^-1 degrees celsius to the -1.
• Density is 1g/cm^-3
C =4.2 X 1000= 4,200 Joules
Plastic container is used because plastic has a NEGLIGIBLE specific heat capacity, i.e. we can
assume the container itself doesn’t absorb heat.
Mass of the solution = 1 gram per cm^3 density X (200+200)cm^3 = 400g = 0.4KG
Heat liberated = M X C X temp rise = 0.4 X 4,200 X 5.5 = 9,240 Joules
Number of moles of H2SO4 Liberated = (volume X Molarity) divided by 1000 = (200 X 0.4)/ 1000 =
0.08 Moles
0.08 Moles of H2SO4 Liberates 9240 joules
1 mole liberates 9240/0.08 joules/ 115,000 joules
115,000 joules is 115.5 KJ
H2SO4 + 2NaOH ------> Na2SO4 + H20
i.e. 2H+ + 2OH- -----> 2H2O
Heat of neutralisation is when 1 mole of H+ Ions react with 1 mole OH- ions, here there are 2
moles.
115.5/2 = -57.75 KJ molˆ-1
Heat of neutralisation is half the heat of reaction here
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The heat of formation of a compound is the heat change that takes place when one mole of
a compound in its standard state is formed from its elements in their standard states.
Standard state is at 25 degrees and at 1 atmospheric pressure or 101 KPa
2C + H2 ------> C2H2 deltaH= 233kJmol^-1 you will be required to write down heats of formation
and sometimes fractions will be necessary.
1/2N2 + 3/2H2 -----> NH3
Hess’s Law states that if a chemical reaction takes place in a number of stages, the sum of
the heat changes in the separate stages is equal to the heat change if the reaction is
carried out in 1 stage.
A -----> B ------> C -----> D
Delta H of A --> D = deltaH of A-->B + DeltaH of B-->C + DeltaH of C--->D
May be used indirectly to measure the heat of reaction of a chemical reaction that may be difficult
to measure.
1. Calculate heat of formation of a compound using other
heats of formation and one heat of reaction
(i) C + O2 ----> CO2 deltah= -393
(ii) H2 + 1/2O2 --> H20 deltah=-286
(iii) CH4 + 2O2 --> CO2 + H20 deltah=-879
calculate the heat of formation of methane.
what we need: C + 2H2 ----> CH4 deltaH= ?????
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Start by introducing C - C + O2 ---> CO2 deltah=-393
introduce 2H2 by multiplying (ii) by 2 : 2H2 + O2 ---> 2H20 deltah= -572
add both equations here
C + 2H2 +202 ----> CO2 + 2H20 deltah = -393-572 = -965
We need CH4 on right hand side so REVERSE equation (iii) and add to the previous
equation:
reversed - CO2 + 2H20 ----> CH4 + 2O2 deltah= +879
Add - CO2 + 2H2 + 202 +2H20 + C ---> CH4 + 2H20 + CO2 + 202
this leaves us with
C + 2H2 ----> CH4 deltaH = -965 + 879 = -86
2. Calculate Heat of reaction using heats of formation of
reactants and products.
This is the same as above except a more complex equation IS GIVEN to us
with heats of formation of its elements.
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Sources of Hydrocarbons
Hydrocarbons
• compounds consisting of hydrogen and carbon only, bonded together covalently.
• important as fuels and feedstock for the chemical industry.
Coal, Natural Gas and Petroleum
• sources of hydrocarbons
• formed from the compacted remains of dead plants of animals which have been
fossilised
• crude oil and natural gas = marine animals and plants
Decomposition as Methane Sources
• anaerobic decay - animal waste, vegetation, rubbish dumps
Hazards of Methane Production
• extremely explosive
Structure of Aliphatic Hydrocarbons
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Aliphatic
• hydrocarbons which do not contain a benzene ring
Homologous Series
• a homologous series is a family of organic compounds with the same general formula,
similar chemical properties, gradations in physical properties, and each member differs
by a CH2 unit
No. of Carbons Root
1 Meth
2 Eth
3 Prop
4 But
5 Pent
6 Hex
7 Hept
8 Oct
9 Non
10 Dec
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Alkanes - names, structural formulas, isomers (to C-5)
• -ane
• CnHn+2
• saturated (only single bonds)
• making isomers: shorten chain by one, add methyl group to an inner carbon
• tetrahedral shape
Alkanes - physical properties
• lower (up to butane) - gases @ rt
• middle (up to C15) - liquids @ rt
• high (C15+) - waxy solids @ rt
• longer chains ➝ stronger van der Waals’ ➝ higher boiling point
• non-polar - cyclohexane and methylbenzene
Alkenes - names, formulas, isomers to C-4
• CNH2N
• C = C (unsaturated)
• lowest member is ethene
• isomers of butene: but-1-ene, but-2-ene, 2-methylpropene
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• lower - gases,
• higher - liquids or solids
• non-polar or slight polarity
• longer chains ➝ stronger van der Waals’ ➝ higher boiling point
Prep and Properties of Ethene
• ethanol is dehydrated using hot aluminium oxide (white powder)
• non-polar so collected by displacement of water
• C2H5OH ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⟶ C2H4 + H2O
•
•
(III) combustion: sooty, smoky flame. Limewater ⟶ milky
(IV) unsaturation: bromine water ⟶ cloudy
(V) unsaturation: acidified potassium manganate(VII) ⟶ cloudy
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Alkynes - Ethyne / Acetylene
(VI) C2H2N-2
(VII) C≣C (unsaturated)
(VIII) lowest member is ethyne
(IX) longer chains ➝ stronger van der Waals’ ➝ higher boiling point
(X) lower - gases,
(XI) higher - liquids or solids
(XII) non-polar or slight polarity
(XIII) uses: cutting metal and welding - oxyacetylene torch
Prep and Properties of Ethyne
(XIV) impurities: calcium sulfide & calcium phosphide ⟶ phosphene, hydrogen sulfide
(XV) acidified copper sulfate soln to remove impurities
(XVI) calcium dicarbide & water
(XVII) CaC2 + 2H2O ⟶ C2H2 + Ca(OH)2
2.
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(iv) liquid in dropping funnel = water
(v) X = calcium dicarbide
(vi) Y = acidified copper sulfate soln
(vii) colourless, sweet smell
(viii) combustion: explosive, basic
(ix) unsaturation: bromine water
(x) unsaturation: potassium manganate(VII)
Aromatic Hydrocarbons
Structure of Benzene, Methylbenzene and Ethylbenzene
(xi) carbon-carbon bonds are intermediate between single and double bonds
(xii) (due to) delocalised pi electron cloud
(xiii) note: benzene is carcinogenic
3.
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4.
Uses of Aromatic Compounds
• methyl benzene - industrial solvent - dissolves non-polar solvents
• martius yellow - dye
• folic acid - pharmaceuticals
• morphine - pain killer
• diuron - herbicide
• phenolphthalein & methyl orange - acid-base indicators
• aspirin - pain killer (non-carcinogenic)
Physical Properties
• non-polar
• lower - liquids
• higher - solids
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